Amine-modified thermoplastic phenolaldehyde resins, and method of making same



AMlNE-MODIFIED THERMQPLASTIC -PHENOL' ALDEHYDE RESWS, AND METHOD MAK- INGSAME No Drawing; Original application ctober1 2f1953l; Se-

rial No. 383,928." Divided and this-application December 6,1956, Serial No. 626,615 I 9 Claims. omen-#53 Attentionfis directed torny c'o-pending applications,

a Serial Numbers.288,742, through,288,746, inclusive, filed May 19, 1952, now abandoned, and a division-of my copending, application Serial No. 383,928, filed OctOber 2, 1953, Patent No. 2,792,366. ,The firstof said co-pending, applications is directed to'a process, for breaking pe troleum emulsions employing a demulsifier including. productsobtained by condensing certain phenolraldehyde resins, .therein described in detail, with certain basic ,non-, hydroxylated secondary monoamines, also therein de-. scribed in detail, and formaldehyde. p 1 I, The second application, is similar to thefirst except that themoncamines employed as reactants .are hydrox-v ylated instead of being nonhydroxylate'd. The third {ap-. plication is similar to the first one insofar that ,no'nh'ydroxylated polyarnines areuemployed as'reactants. The

United States PatentO ice in which R represents any appropriate hydrocarbon radical, such as an alkyl; alicyclic, arylalkyl radical, etc., free from hydroxyl radicals. The only limitation is that the radical should not beta negativecradical, which con- 'siderably reduces the basicity ofthe amine, such as an aryl radical or an acyl .radical. Needless to say, the two occurrences of R may jointly represent a single divalent radical instead of two monovalent radicals. This is illustrated by morpholineand. piperidine. The introduction of two such amino radicals into a comparatively small resin molecule, for instance, "one having 3 to 6 phenolic nuclei as specified; alters the zresultant product in a number of ways. Inv the afirst place, .a basic .nitr o-n gen atom, of course, addsahydrophile effect; in the sec ond tplace,"' depending on the size :ofrthe-radical, R, there may:be-aucounterbalancing hydrophobe effect or one in which the hydrophobe effect. more than counterbalances phile effect. a.

fourth application is concernedwith 'h ydroxylatedjpoly amines as reactants and the last application is concerned with amines having' a cyclic ami'dine group in there;

' actant regardless of whether it is hydroxylatedv ornot. I

The present application is differentiated from the aforementioned five applications 'in'that the aldehydeused,

instead of beingiormaldehyde, isglyoxal; StatedQanother way, this invention is concerned .with'certain heatstable oxyalkylation-susceptible resinous condensation products obtained by condensing certain phenol-aldehyde resins, hereinafter described in detail, .with certain basic secondary amines, also ,hereinafter'described in detail, and glyoxal. i

For purpose of vert momentarily to the products described in the five aforementioned co-pending applications, Serial N'os.288,-

illustration it may be simpler todi' 742 through and including 288,746, inclusive, and for sake of simplicity to the first one, i. e., Serial No. 288,-

742, in which the amine reactant is a nonhydroxylated monoarnine. For purpose of simplicity the invention described in said co -pending application, Serial No. 288,- 742, maybe exemplified by an idealized formula, as ,fol-

' erably not over 14 carbon atoms, and n generally-is a small Whole number varying from 1 to 4. Inthe resin structure it'is shown as being derived from formaldehyde although obviously other aldehydes are equally satisfactory. The amine residue-in the above structure is derived from a basic amine, and usually a strongly basic amine, and may beindicated thus:

the hydrophile effect of the nitrogen atom. Finally, in such cases whereiRt contains one or moreoxygen atoms, another. effect-is introduced, particularly another hydro-:

1 Suclrzcondensates; e., the "condensates 'of Serial No. 288,742; and :iin :fact;.th'e.einstant condensates, ,are .ob-. tairied ifromephenol-aldehyde resins. ltziswwell known that one-can readily-r purchase on theopenmarket, or pre.-- pare fusible,-:1organic isolventesoluble, twater-insolubleeresin polymers of a composition approximated inaanidealized form by the formulas:

In the above formula n represents a's'mall whole number varying from l'to 6, 7;or-8, or more, up to :probably 10 or, 12 units, particularly when the resin is,subjected, to

heating undera vacuum-as described in the'literature.v -A limited sub-genus is .in the instance -,of"low molecular mole of glyoxal to replace 2smoles of formaldehyde, it

becomes apparent that certain. other modifications can and do take place withthe result that one obtains a mole- .culeghaving a differentvstructure and inmanyinstances acornparatively higher molecular Weight; ;All that is necessary is to reconsider the condensate inzterms-of the overfsimplified structure previously noted, 'toavvit:

For-convenience, this formula can be abbreviated somewhat, thus:

aszazas I resin, the-secondary amineand formaldehyde. J The reference is as follows:

In conducting reactions of this kind one does not necessarily obtain a hundred percent yield for obvious reasons. Certain side reactions may'take place. For instance, 2 inoles'of aminemay combine with one mole of the aldehyde, or only one moleof the amine may combine'with'the resin molecule, or even to a very slight extent, if 'at all, 2 resin units may combine without any amine in the reaction product, as indicated in the following formulas: 7 r

When formaldehyde is replaced by glyoxal, in light of what hasbeen said it becomes apparent that the three above formulas could be written showing dimeric or' tri meric forms'of each structure rather than the monomer.

Over and above this combinations could take place between any one of the three above or any one of the three with the condensate previously depicted.

In any event, to the extent that in a reaction mass formaldehyde is replaced by glyoxal it becomes apparent that a more complicated and an entirely different'structure, or structures-are obtainable. In many instances where formaldehyde gives atcondensate which is a highly viscous liquid the use of glyoxal results in a solid. Furthermore, the molecular weight to the extent that its determination can be made or approximations can be made, seem to be distinctly higher in molecular weight. In any event, the condensates so obtained "are dilferent in character and for some purposes particularly after oxyalkylation with ethylene oxide, propylene it oxide, butylene oxide, glycide, or methylglycide are particularly elfective for the resolution of petroleum emulsions. Indeed, in many instances-the oxyalkylation derivatives are distinctly more effective than the comparable products derived from used.

For purposes of convenience what is said hereinafter will be divided into five parts: Part 1 is concerned with able "for condensationyi g:

condensates in which formaldehyde is phenol aldehyde resins suit- I i Part 2 is concerned with suitable secondary amines which can be employed in conjunction with the resins in the condensation procedure;

Part 3 is concerned with'the condensation procedure as such; 7 V r Part 4' is concerned with the uses of the condensates for the resolutionof petroleum emulsions, and

Part 5 is concerned with uses for the condensates for purposes other than de'mulsification, and particularly for their use as .initial raw materials which are subjected to oxyalkylation. r

PART 1 This. part is concerned with the preparation of phenolaldehyde resins of the kind described in detail in U. SI Patent No. 2,499,370, dated March 7, 1950, to De Groote and Keiser, with the following qualifications; said aforementioned patent is limited to resins obtained from difunctional phenols having 4 to 12 carbon atoms in the decylphenol' or octadecylphenol.

. 2 ,499,365, 2,499,366,.and 2,499,367, all dated March 7,

1950, to De Grooteand Keiser. These patents, along with the other two preViOusIy' mentioned patents, de' scribe phenolic" resins of the kind herein employed as initial materials. ,i V T 'For practical purposes, the resins having 4 to 12 carbon atoms are'most satisfactory, with the additional C carbon atoms also being very satisfactory. The increased cost of the C and C 5 carbon atom phenol renders these raw materials of less importance, at least at the present time.

Patent 2,499,370 describes in detail methods of preparing resins 'useful as intermediates'for preparing the products of the present'application, and reference is made to that-patent for such detailed description and to Examples la through 103a of that patent for examples of suitable'resins;

j .As previously noted, the hydrocarbon substituent in the phenol mayv have a's'many as 18 carbon atoms, as illustrated by tetradecylphenol, hexadecylphenol and octadecylphenol,-reference. in each instance beingto the difunctional phenol, such as the orthoor para-substituted iphenol'orainixture of the same. Such resins are derscribedals'o in issued patents, for instance, U. S. Patent sNo. 2,499,365, dated March "7, 1950, to De Groote and Keiser, such as'Example 71a.

' Reference has been made toanearlier formula which was. in essence ,an over-simplification representing a phendlformaldehyde resin. Actually, some other aldehyde, such as acetaldehyde, propionaldehyde, or b'utyraldehyde, may be used, The resin unit can be'exemplified in which R"? the divalent radical obtained from the prepared by using a strong acid as a catalyst, such strong erable that the base be neutralized although we have found that sometimes the reaction described proceeded '5 more rapidly in the presence of "aj-small amount of free base. The amount may be as small as a 200th of a pera cent and as much as a few tenths of a .percent. Sometimes moderate increase in caustic soda and caustic potash maybe used; 'However, the most desirable procedure in practically every'caseris to'hav'eithe resin-neutral,

In preparing resins one does not get a single gPQlymer,

, i. e., one having just 3 units, or just =4 units, or just 5 units, or just 6 units, etc. It isusually a mixture; for instance, one approximating '4 phenolic nuclei will have some trimer and pentamer present. Thus, the molecular weight may be-sueh that it corresponds'to a fractional value for n as, for example, 3.5, 4.5 or 5.2.

In the actual manufacture of the resins I found no 7 reason for using other than. those which are lowest in price and most readily available commercially. For purpose of convenience suitableresins are characterized in the following table:

' TABLE 1 M01. wt

Ex- Position R of resin ample R of R derived 'n molect 1e number from (based on n+2) Phenyl Para Formal- 3.5 992.5 dchyde. Tertiary b tyl do o r r 3.5 882.5 Secondary bi:ty1- Ortho .do 3.5 882.5 Cyclohexyl Para .do 3.5 1,025.5 Tertiary amyl do o 3.5 959.5

Mixed secondary Ortho... do 3.5 805.5

and tertiary amyl.

Tertiary amyl 3.5 1,022.5 Nonyl 3.5 1. 330.5 Tertiary butyl. 3. 5 1, 071. 5

Tertiary amyl .d 3.5 1,148.5 Nonyl. ..do do 3.5 1,456.5 Tertiary butyl do. Propional- 3.5 1,008.5

dehyde. Tertiary amyl .do o 3.5. 1,085.5 Nonyl ..do do 3.5 1,393.5 Tertiary butyl 4. 2 996.6 Tertiary amyl 4.2 1,083.4 Nonyl 4.2 1,430.6 Tertiary butyl. 4.8 1,094.4 Tertiary amyl 4. 8 1, 189. 6 Nonyl 4. 8 1, 570. 4 Tertiary amyl. 1. 5 604.0 1.5 646.0 1.5 653.0 1.5 688.0 5

PART 2 As noted previously, a variety of secondary amines free I 'from a primary amino group may be employed. These amines-fall into five categories,-as indicated previously.

One category consists of strongly baslc secondary monoamines free from-hydroxyl groups whose'composition may be indicated thus:

' or a similar procedure.

in which R representssa*monovalent-alkyl, ,alicyclic, arylalkyl radical and may be heterocyclic in a few instances as in the case of piperidine and a secondary amine derived f-rom furfurylamine by methylation or ethylation,

Another example of a heterocyclic amine is, of course, morpholine.

The secondary-amines most readily available are, of course, amines suchias dimethylamine,methylethylamine, diethylamine, dipropylamine, ethylpropylamine, dibutylamine, diamylamine, dihexylamine, dioctylamine, and dinonylamine- Other amines include bis(1,3-dimethylbutyllamine. There are, of. course, a variety of .primary amines which can be reacted'with an alkylating agent such as dimethyl sulfate, diethyl sulfate, an alkyl bromide, an ester 'of sulfonic-acid, etc., to'produce suitable aminesiwithin the herein specified limitations. For example, one canmethylate alpha-methylbenzylamine, or benzylamine itself, to produce a suitable reactant. Needless. to say, one can use secondary amines 'such'as dicyclyohexylamine, idibutylamineor amines containing oneicyclohexyl group andone alkyl group, or one benzyl group androne. alkyl group, such as ethylcyclohexylamine, ethylbenzylamine, etc.

Other suitable compounds are exemplified by Other somewhat similar secondary amines are those of the composition a RO(OHi)5 as described in U. S. Patent'No. 2,375,659, dated May 8, 1945, to Jones et al. In the above formula R may be methyl, ethyl, propyl, amyl,-octyl,' etc. 7

Other amines can be obtained from products which are sold in the open market, such as may be obtained by alkylation of cyclohexylmethylamine or the alkylation of similar primary amines, or, for that matter, amines of the kind described in U. S. Patent No. 2,482,546, dated September 20, 1949, to Kaszuba, provided there is no negative group or halogen attached to the phenolic nucleus. Examples include the following: beta-phenoxyethylamine, gamma-phenoxypropylamine, -beta-phenoxy-alpha-rnethylethylamine, and beta-phenoxypropylamine.

Other suitable amines are the kind described in British Patent No. 456,517 and may be illustrated by (021150 C2H4O C2H4) NH HO otn i (011150 011140015110 022m H0 CzHt (oirnoomcmomo ongoncrn (omoomomocmqmo01110111) I f or comparable compounds having' two groups of different lengths as in V V V V noou iomoornomoomomr Other examples of suitable amines include alpha-methylbenzylamine and nionoethanolamine; also 'amines obtained by treating cyclohexylmethylamine with one mole of an oxyalkylating agent as previously described; betaethylhexylbutanolamine, digiycerylamine, etc. ,-Another type of amine which is of particular interest because it includes a very definite hydrophile groupincludes sugar amines such as glucamine, galactamine and fructamine, such as N-hydroxyethylglucamine, N-hydroxyethylgalactamine, and N-hydroxyethyltructamine.

Other suitable amines may be illustrated by Polyamines free from a hydroxyl group may be illustrated by the following:

- CH3 7 1 on;

NcsHiNcaHiN (CH3)zNCaH4NC2H-1N(CH3)2 02H; CzHs N C2H5NC2 H4N CHa C 2H: t

/NC2H4O C2H4N CH1 0H:

H /NpropyleneNpropyleneN H r her by a compound such as A 'The fo'urthcategory consists of polyamines having hydroxylated groups which may be characterized by the following: g a i Y I orro:eu

, V ,NCVZH4NCQH4VN HOCQH; C2H4OH 2 4)aNC2H4NC2H4 z 4 )2' 02H; Ci a NciHiNoiHiN uo'oini 0211401:

on; CH3 NC2HiOCzH4N HOCzH4 CZHiOH CzHa C2 5 H 0 C 2H4 C :H4 0 H CH3 CH; H

NpropyleneNpropyleneN V 'Hoonan CHs CH3 CH3 Suitable cyclic amidines which may or may not have a hydroxyl group but are free from primary amino groups may be illustrated by the following: 2-undecy1imidazoline Z-heptadecylimidazoline 2-oleylimidazoline V 1-N-decylaminoethyl,2-ethylimidazoline 2-methy1,1-hexadecylaminoethylaminoethylimidazoline 1-dodecylaminopropylimidazoline l-(stearoyloxethyl)aminoethylimidazoline 1-stearamidoethylaminoethylimidazoline 1-(N-dodecyl)-acetamidoethylaminoethylimidazoline 2-heptadecyl,4,S-dimcthylimidazoline 1-dodecylaminohexylimidazoline 1-stearoyloxyethylaminohexylimidazoline 2-heptadecyl,l-methylaminoethyl tetrahydropyrimidine 4-methyl,2-dodecyl,l-methylaminoethylaminoethyl tetrahydropyrimidine ,CHs

CzHrOH CzHiOH A compound having no basic'secondary amino radical but a basic primary amino radical can be reacted with a mole of an alkylene oxide, such as ethylene oxide, propylene oxide, 'glycide, etc., to yielda perfectly satisfactory reactant for the herein described condensation procedure. This can be illustrated in the following man- 7 :2HLNH2 2-heptadecy1, l-aminoethylimidazoline generic mixtureiexcept interms of the process-itself.

ta ined from glyoxal and not formaldehyde.- s -peaking,

even by using formaldehyde.

whichca'n i'be reacted'with a si' 'gle'm'ole of ethylene oxide, for example, -,toprb'duce 'th'e hydfdxy ethyl derivative of Z-heptadecyl,lamirioethylimidazoline, which can be illustrated by the'followingfor'mula:

Other reactants maybe employed in connection with an initia'l reactant of "the kind described above, to wit, 2- heptadecyl,l-aminoethylimidazoline; for instance, reaction with an .alkylene iminesuch as ethylene imine, propylene imine, etc. If reacted with ethylene imine the net result is to convert a primary amino radical into a secondary 7 amino radical and also to introduce a new primary amine group. If ethylene imineis employed, the net result is simply to convert Z-heptadecyl, l-aminoethylimidazoline 20 into Z-heptadecyl, l diethylenediaminoimidazoline. Ho'w-: ever, if propylene imine is used the net result is a com-' pound which can be considered as being derived hypothetically from a mixed polyalkylene amine, i. e., one having both ethylene groups and a propylene group-between nitrogen atoms. p 1

PART 3 The products obtained by the herein described processes represent cogeneric mixtures which are the result of a condensation reaction or reactions. Since the resin molecule cann-ot be defined satisfactorily by formula, although it may be so illustrated in an idealized simplificatiomit is difficult to actually depictthe final productbfT'theco-f The herein described amine-modified resins 'are ob- Generally I the objective in the preparation of these aminemodified resins is'to obtaina heat-convertiblecompound" It is'not-necessa'ry to point-1.v out the complications involved when glyoxal'is used. Seef, for example, U. S. Patent No. 2,031,557 tc'Bruson. Since the condensation products obtained are not hreat-con: 7 vertible and since a. temperature up r0150 C(or there-q 3 abouts may be employed, it is obvious that the'proc'edure becomes comparatively simple. {lndeedfperhapsmo'description is necessary over and 'above what has been said previously,

in light of subsequent examples. However, for purpose of'clarity the followingdetails'areinclude'dt A convenient piece of equipment forpreparation -of these cogeneric mixtures is a resin pot of the kind de-E scribed in afo-rementioned U. S. Patentv No.;2,499,3.68.. In most instances the resin selected is not apt to be a fusible liquid at the early. or low temperature stage of reaction if employed as subsequently described; in fact, 55

i usually it is apt to be a solid at distinctly higher temperatures, for instance," ordinary room .temperature. Thus, I have found it convenient tame a solvent and particularly one which can be removed readily at a comparatively moderate temperature, forinstance, at 150 C. A suitable solvent is. usually benzene, xylene, or a comparable petroleum hydrocarbon or a mixture of such or similar solvents. Indeed, resins which are not soluble except in oxygenated solvents or mixtures containing such solvents are not here included as raw materials. The reaction can be conducted in such a way that the initial reaction, and perhaps the bulk of the reaction, takes place in a polyphase system. However, if desirable, one can use an oxygenated solvent such as a low-boiling alcohol, including ethyl alcohol, methyl alcohol, etc. Higher 79 alcohols can be used or one can use a comparatively nonvolatile solvent suchas' dioxane or the diethylether of ethyleneglycol. One can also use a mixture of benzene or xylene and such oxygenated solvents. Notefthatl the use of such oxygenated solvent is not required in. the 75 1 by' the use of formaldehyde or furfural.

suggested-previously, this apparently is due to the difuncresin selected and the amine 'uct 'or reaction mass on a solvent-free basis is apt to be harder than the original resin itself. true-when all the amino hydrogen atoms present in the amine have entered into'reaction.

sense that it is not'ne'cessary'to'use an initial 'resin' which is soluble only in anoxygenated solvent as noted,'and it is not necessary to have a single phase system for reaction. p I Q v 'Glyoxal is available'as"a30% aqueous solution. In this way it'is compa'rable'to formaldehyde which is available as a 37% aqueous solution, and is sometimes used in more dilute'form. Ihave found no difficulty in pro- 'rnoting the condensation reaction although at times it is desirable to addsome solventhaving a'common'solvent eifect. Thus an oxygenated solvent may or may not be employed. Such'solvent may be employed in combination with a.hydr"ocarbon solvent such as xylene. However, if the'reaction-mass is going to be subjected to some further reaction where the solvent may be objectionable as in the case of ethyl or hexyl alcohol, and if there is to lie-subsequent oxyalkylation, then, obviously, the alcohOlSuSl'lOllld not be used or else it should be removed. The .fact that an-oxygenated solvent need not be employed; of'course,'is 'an-advantage for reasons stated.

vAnother factor; as fares the selection of solvent goes,

is whether or notithe'jcogeneric mixture obtained at the endo'fihereact on-isto be used as such or in the salt form. The cogenericlrnixtures obtained are apt to be zs'olidsor thick viscousiliquids in which there is some change from the initial resin itself, particularly if some of the'initial solventisapt to remain without complete removal. Even if one starts with a resin which is almost water-white -incolor, the condensation products obtained are invariablydark and particularly reddish or darkred in color.

By and'large, themelting point of the condensate is apt to-be higher than of comparable condensates obtained As has been tional property of .glyoxal. Indeed, depending on the selected the condensate prod- This is particularly The products obtained, depending on the reactants selected, may be water-insoluble, or water-dispersible, or water-soluble, orclose to being water-soluble. Water solubility is enhanced, of course, by making a solution in the acidified vehicle such as a dilute solution, for instance, a 5% solution of hydrochloric acid, acetic acid, hydr'oxy-acetic acid, etc. One also may convert the finished product into salts by simply adding a stoichiometric amount of any selected acid and removing any water present by'refluxtng with benzene or the like. In

fact, the'selection of the solvent employed may depend in part whether or not'the product at the completion of the reaction is to be converted into a salt form. I

' In the next succeeding paragraph it is pointed out that frequently it is convenient to eliminate all solvent, using a temperature of not over 150 C. and employing vacuum if required. This applies, of course,'only to those circumstancesawhe're it is desirable or necessary to remove the solvent. Petroleum solvents, aromatic. solvents, etc., can be used. The selection of solvent, such as benzene, xylene or the like, depends primarily on cost, i.,e., the use of the mostfeconomicalsolvent and also on three other factors, two of which have been mentioned previously; "((1) is the solvent to remain in the reaction mass without removal? (b) is the reaction mass to be subjected to further reaction in which the solvent, for instance, an alcohol, either low boiling or high boiling,

'might interfere as in the caseof oxyalkylation2ahd the third factor is this (c) is an etfortto be made to purify the reaction mass by the usual procedure as, for example, a water-washto remove any unreacted low molal soluble amine, if. employed and present after reaction? Such procedures are well known and, needless to say, certain solvents are more suitable than 'others'. Everything else being equal,I havefound xylene the most satisfactory case may be, from 135 to 160? C. Where the amine following table.

evaporated to eliminate the xylene. The resultant prod:

uct was a highly viscous, tacky material, being black in color with a reddish tinge. I

Similar products were prepared as indicated in; the

TABLE II Solvent Max. R sin 7 Glyoxal (xylene Time temp. Ex. N o. amt; Secondary amine Amt, aq. unless period, during grams grams sol.) otherwise hrs. reaction,

grams noted), 0.

grams 1b 175 Di-isopropylamine 61 58 170 7 145 150 Di-n-butylamine. 65 48 160 6 160 150 Di-ethylamine 37 48 155 5 143 150 Di-ey lohcxylamine.-. 91 48 155 7 170 300 Morphnline 87 96 305 6 e 145 300 .Di-2-e-thylhexylamme. 241 96 290 4. 5 163 225 B i i .3-dini thyl-butyl)amine.. 139 72 235 225 Di-isopropanolamine 72 230 3 160 r 225 a-Methylbenzyl-ethano1amine- 124 72 235 3 157 225 Di-eihanolamiue 79 72 220 2. 5 158 225 Aminoethyl vthanola-mine. 78 72 230 2 225 Diethnnolamine 79 72 "55470 3 100 225 Dictlianommine." 79 72 55-170 3 98 225 :Diethanolamine e- 131. 5 128 "55470 3 99 225 .Diisopropanolaminenu 174 128 235 1. 75 130 236 Di-isopropanolamine 61 58 231 7 197 Di-n-butylamineun' 65 48 192 6 160 197 Dl-ethylamineuu 37 48 203 5 145 197 Di-cyelohcxylamine- 91 48 185 7 165 393 Morpholine 87 96 384 6. 5 393 Di-(Z-ethylhexybamine 241 96 398 5. 0 170 197 N-meth ylaniline. 54 48 102 4 170 295 DHbeta-phen ylethyDa 169 72 300 4. 5 295 Di-isopropanolaluhle 100 72 200 3 155 225 Di-ethanolamine 79 72 305 2. 75 158 188 Di-isopropylamin 61 58 220 8 145 188 Dr-mbutylamtne 65 I 48 178 5 162 188 Di-ethylamine. 37 48 180 V 6 145 374 Di'cyclohexyla 91 48 196 7 163 374 Morph0line 87 p 96. 37 6.5 155 188 Di-(l-etliylhe. 241 96 378 4.5 168 280 N-methylaniline e 54 48 198 5 170 280 Di-(beta-phenyleth )a 169 72 290 4. 5 158 280 Di-isopropanolamine 100 72 270 3 155 280 Di-ethanolamln e 79 72 270 2. 75 158 powdered sodium methylate.

In Examp es 12b,

33b and 14!) indicated by the double j asterisk. the so vent was a mixture of 170 parts of benzene and 55 parts of xylene.

The molar ratio of resin to amine to aldehyde was 1 to 2 to 1, except in Examples 145 and 1511 where the ratio was 1 to 3 5 to l 75 in botli instances.

In Examples 11) thr'ugh 155 one identified as Example 28athe resin employed was the a In Examples through 251) the resin employed was the one identified as Example 32a, and in Examples 205 identified as Example 39a.

has a comparatively low basicity I have sometimes added a small amount or approximately 1% of sodium methylate.

However, using a xylene-benzene mixture, for instance,

approximately partsof benzene and 35 parts of Example 1b The resin employed was the one previously designated as 28a and had a molecular weight of approximately 600. grams of this resin were dissolved in an equal weight of xylene and .61 grams of di-isopropanolamine added. 58 grams of 'glyoxal (30% aqueous-solution) were added and themixture stirred for about 30 minutes and then the temperature allowed to rise to 140 C.

through 3511 the resin employed was Furthermore, the situation becomes even more complicatedif the ratios are changed to correspond to ratios described in. my co-pending application, Serial No 376,240, lthe reare: described anumber of complicated condensates ed. August 24, 1953. In this particular instance gar-sa as in which 3% molesof 'diethanolamine; or the like, Bl moles of formaldehyde, and one mole of the phenolaldehyde resin, are employed. If ,correspondin'gcondensates are prepared, replacing *3' 'moles of formaldehyde by 1% moles of glyoxal, a variety ofgcompounds are obtained which have unusual structure but are still organic solvent-soluble and susceptible to oxyalkylation. Indeed, another variety of somewhatv more complicated materials are obtained by using as the amine reactant di(hydroxyethyl)'N,N-ethylene diamine having the following structure: 7

H CZHgOH alkylation. The products so obtained find utility in various arts.

PART 4 As to the use of conventional demulsifying agents reference is made to U. S. Patent No. 2,626,929, dated January 7, 1953, to De Groote, and particularly to Part 3. Everything that appears therein applies with equal force and effect to the instant process, noting only that where reference is made to Example 13b in said text beginning in column 15 and ending in column 18, reference should be to Example 8b, herein described.

PART

The products described in Part 4 have utility in at least two distinct waystheproducts as such, or in the form of some simple derivative, such as the salt which can be used in numerous .arts subsequently described. Also, the products can serve as initial materialsfor more complicated reactions of the kind previously mentioned, to wit, they may be subjected to oxyalkylation, particularly oxyethylation, or oxypropylation or oxybutylation.

to give products which are not only valuable for the purpose described in regard to the parent material or the salts of the parent material, but also for other purposes. Likewise, since the tertiary amino nitrogen atom is present the products can readily be reacted with suitable reactants such as chloroacetic acid esters, benzylchloride, alkyl halides, esters of sulfonic acids, methyl sulfate, or the like, to give quaternary ammonium compounds which are used, not only for the purposes herein described, but also for various other uses.

In such instances where the amine contains a hydroxyl group the product is susceptible to reactions involving the hydroxyl radical, particularly acylation reactions, etc., i. e., reactions involving the use of either monocarboxy acids which may be low molal or high molal, and polycarboxy acids of the kind previously enumerated.

The products herein described as such and prepared in accordance with this invention can be used as emulsifying agents, for oils, fats and waxes, as ingredients in insecticides compositions, or as detergents and wetting agents in the laundering, scouring, dyeing, tanning and mordanting industries. They also may be used for preparing boring or metal-cutting oils and cattle dips, as metal pickling inhibitors, and for pharmaceutical purposes.

Other uses include the preparation or resolution'of petroleum emulsions,.whether of the water-in-oil type 1'4 or oil-in-water type. They may be'usedas additives in connection with other emulsifying agents; they may be employed to contribute hydrotropic effects; they may be used as anti-strippers in connection with asphalts. They may be used to prevent corrosion, particularly the corrosion of ferrous metals for various purposes and particularly in connection with the production of oil and gas, :and also in refineries where crude oil is converted into various commercial products... The products may be used industrially I to; inhibit "or stop :microorganic growthor other objectionable lower forms'of life, such as the growth of;algae,t;or thedike; they maybe usedto inhibit thegrowth of bacteria,;molds-, ,etc.; they are valuable additives to lubricating oils, bothithose derived from petroleum and syntheticuilubricating;oils,and also to hydraulic brake-fluids ofjthe aqueous or nonaqueous type. Some have-definite :anti-corrosive action. They may be used in connection with other. processes where they are injected into: an 'oil.or gas well for the purpose of removing amudfsheath, increasing the ultimate flow or fluid from the surrounding..strata,.and particularly in the secondary recovery operations using aqueous flood waters. They may be used also in dry cleaners soaps.

With regard to the above statements, reference is made particularly to the use of the materials assuch, or in the form of a salt; the saltform refers tow a salt involving either one or both basicnitrogen. atoms. Obviously, the salt form involves a modification :in which the hydrophile character can either be 'increasedzor decreased and, inversely; the hydrophobe character can be decreased or increased. For example, neutralizing the product with practically any low molalqacidysuch as acetic acid, hydroxy acetic acid, lactic acid,,or nitric acid, is apt to markedly increase the hydrophile effect. One may also use acids of the type in which R is a comparatively small alkyl'radical, such as methyl, ethyl or propyl. The hydrophile effect may be decreased and the -hydrophobe-"etfect increased by neutralizing with a monocarboxy detergent-forming acid. These are acids'whichhave at least 8 and not more than 32 carbon atoms. They are obtained from higher fatty acids and include also resin acids such as abietic acid, and petroleum acids such as naphthenic acids and acids obtained by the oxidation of wax. One can also obtain new products having unique properties by combination with polybasic acids, such as diglycolic acid, oxalic acid, dimerized acidsfrom linseed oil, etc. The most common examples, of course, are the higher fatty acids hav- 7 ing generally 10 to 18 carbon atoms. I have found that a particularly valuable anti corrosive agent can be obtained from any suitable resin and formaldehyde pro vided the secondary amine is hydroxyethyl cyclohexylamine. The corrosion inhibiting properties of this compound can be increased by neutralization with either one or two moles of an oil-soluble sulfonic acid, particularly a sulfonic acidof the type known as mahogany sulfonic.

acid.

I have found the products herein described are of unusual utility for preventing the separation of sludge .i fuel oil during storage.

Having thus described my invention,what I claim as: new and desire. to secure by Letters Patent is:

l. The process of condensing (a) an oxy alk'ylationsusceptible, fusible, non-oxygenated organic solvent-solu ble, water-insoluble, low-stage phenol-aldehyde resin having an average molecular weight corresponding to at least 3 and not over 6 phenolic nuclei per resin molecule; said resin being derived by reaction between a difunctional monohydric phenol and an aldehyde having not over 8 carbon atoms and reactive toward said phenol; said resin being formed-in the substantial absence'of in which R is an aliphatic hydrocarbon radical having at least 4 and not more than 24 carbonatoms and substituted in the 2,4,6 position; (b) a basic secondary amine free from any primary amino radical and having not more than 32 carbon atoms in any group attached toany amino nitrogen radical and reactive towards glyoxal; and (c) glyoxal; said condensation reaction being conducted at a temperature sufliciently high to eliminate water and below the pyrolytic point of the reactants and resultants of reaction; and with'the proviso that'the resinous condensation product resulting from, the processi beheatstable and oxyalkylation-susceptible. I I

2. The process of claim 1 with the provisothat-there be an alkanol radical attached'to at least one amino nitrogen atom. 1 V a I 3. The process of condensing (a) an oxyalkylation-susceptible, fusible, non-oxygenated organic solvent-soluble, water-insoluble, low-stage phenol-aldehyde resin having an average molecular weight corresponding to at least3 and not over 6 phenolic nuclei per resin molecule; said resin being derived by reaction between a difunctional'monohydri'c phenol and an aldehyde having not over 8 carbon atoms and'rea'ctive toward said phenol; said re'sinbeingi formed in, the substantial absence of phenols of functionality greater than 2; said phenol being of the formula H 1 a r I 1 a, w v

in which R is an aliphatic hydrocarbon radical having at least 4 and not more than 24 carbon atoms and substituted in the 2,4,6 position; (b) a basic hydroxylated secondary monoamine having not more than 32; carbon atoms in any group attached to the amino nitrogen atom and reactive towards glyoxal; and (c) glyoxal; said condensation reaction being conducted at a temperature sutficiently high to eliminate water and below the pyrolytic point of the reactants and resultants of reaction; with'the proviso that the condensation reaction be conducted so as to produce a significant portion of the resultant inwhich each of the three reactants have contributed part of the ultimate molecule bytvirtue of a glyoxal-derived substituted methylene bridge connecting the amino nitrogen-atom Witha resin molecule; with the-further proviso that the ratio of reactants be approximately 1, 21 and 1 respectively; and with the final proviso that theresinous condensation product resulting from the process be heat-stable and oxyalkylation-susceptible. l

4. The process of condensing ((1) can oxyalkylation-sus ceptible, fusible, non-oxygenated organic solvent-soluble, water-insoluble, low-stage phenol-aldehyde resin having an average molecular weight corresponding to at least 3 and not over 6 phenolic nuclei per resin molecule; said resin, being derived by' reaction between a difunctional, monohydric phenol and an aldehyde having not over 8 carbon atoms and reactive toward said phenol; said resin being formed in the substantial absence of phenols of functionality greater than 2; said phenol being of 'the formula 1 v e 7 in which R is an, aliphatic hydrocarbonradical having at least 4 and notmore than 24 carbon atoms and subdensation reaction being conducted at a temperature sufficiently high to eliminate water and below the pyrolytic pointof the reactants and resultants of reactiom with the proviso that the condensation reaction be conducted so as to produce a significant portion of the resultant in'which each of thethree reactants have contributed part of the ultimate molecule by virtue of a glyoxal-derived substituted methylene bridge connecting the amino nitrogen atom with a resin molecule; with the added proviso that the ratio of reactants be approximately 1, 2 and 1, respectively, with the further proviso that said procedure involve the use of a solvent; and with the final proviso that the resinous condensation product resulting from the process be heat-stable and oxyalkylation-Susceptible.

5. The process of condensing (a) an oxyethylation-susceptible; :fusible, non-oxygenated organic solvent-soluble, water-insoluble;low-stage phenol-formaldehyde resin having an average molecular weight corresponding to at least 3 and not over 6 phenolic nuclei per resinmolecule; said resin being derived by reaction between a difunctional monohydric phenol and formaldehyde;tsaid resin being formed in thesubstantial absence'of phenols of functionality greater than 2;said phenol'being of the formula in which R is an aliphatic hydrocarbon radical having at least 4 and not more than 24 carbon, atoms and substituted in the 2,4,6 position; (b) a basic hydroxylated secondary monoamine having not more than 32 carbon atoms in any group attachedto the amino nitrogen atom and reactive towards glyoxal; and (c) glyoxal said condensation reaction being conductedat a temperature sufliciently high to eliminate water and below the pyrolytic point of the reactants and resultants'of reaction; with the proviso that the condensation reaction be conducted so as to produce a significant portionof the resultant in which a each of the three reactants have contributed part of the ultimate molecule by 'virtueof a -glyoxal-derived substituted methylene bridge connectingthe amino nitrogen atom with a resin molecule; with the added provisothat the ratio of reactants be approximately 1, 2 and 1, respectively; with the further proviso that said procedure involve the use of a solvent; and with the final proviso that the resinous condensation product resulting fromtthe process be heat-stable and oxyalkylation-susceptible.

' 6. The process of 'con densing a) an oxyethylationsusceptible, fusible, non-oxygenated organic solvent-soluble, Water-insoluble, low-stagephenol-formaldehyde resin having anaverage molecular Weight corresponding to at least 3 and not overs phenolic nuclei {per resin molecule; said resin being derived by reaction between a difunctional monohydric phenol and formaldehyde; said resin being formed; in'the substantial absence of phenols of functionality greater th anj2; said phenol being of the formula i I a I OH y ,4 I R V in which-R is an aliphatic hydrocarbon radical having at least 4 andnot more than 14 carbon atoms and substituted in the 2,4,6 position; '(b) a basic hydroxylated secondary monoamine having not more than 32 carbon atoms in any group attached to the amino nitrogen atom and reactive towards glyoxal; and (c) glyoxal said condensation reaction being conducted at a temperature above the boiling point of water and below 150 C., with the proviso that the condensation reaction be conducted so as to produce a significant portion of the resultant in which each of the three reactants have contributed part of the ultimate molecule by virtue of a glyoXal-derived substituted methylene bridge connecting the amino nitrogen atom with a resin molecule; with the added proviso that the ratio of reactants be approximately 1, 2 and 1, respectively; with the further proviso that said procedure involve the use of a solvent; and with the final proviso that the resinous condensation product resulting from the process be heat-stable and oxyalkyla- LiCvIl-SUSCEPlZl'Dlfi.

7. The product resulting from the manufacturing process defined in claim 1.

The product resulting from the manufacturing process defined in claim 3. v

9. The product resulting from the manufacturing process defined in claim 6.

No references cited. 

1. THE PROCESS OF CONDENSING (A) AN ALKYLATIONSUSCEPTIBLE, FUSIBLE, NON-OXYGENATED ORGANIC SOLVENT-SOLUHAVING AN AVERAGE MOLECULAR WEIGHT CORRESPONDING TO AT HAVING AN AVERAGE MOLECULAR WEIGHT CORRESPONDING TO AT LEAST 3 AND NOT OVER 6 PHENOLIC NUCLEI PER RESIN MOLECULE; SAID RESIN BEING DERIVED BY REACTION BETWEEN A DIFUNCTIONAL MONOHYDRIC PHENOL AND AN ALDEHYDE HAVING NOT OVER 8 CARBON ATOMS AND REACTIVE TOWARD SAID PHENOL; AID RESIN BEING FORMED IN THE SUBSTANTIAL ABSENCE OF PHENOLS OF FUNCTIONALITY GREATER THAN 2; SAID PHENOL BEING OF THE FORMULA 